Synthesis of hetarylquinolines proceeding from 2-[(2-methylquinolin-4-yl)sulfanyl]acetohydrazide substituted in the benzene ring

At intramolecular cyclization of phenylhydrazinocarbothioamide in alkaline and acidic media quinolyl-substituted triazoles and thiadiazoles are obtained. Quinolyl-substituted thiazolidines and thiazolidinones were obtained at interaction of phenylhydrazinocarbothioamides with bromoacetophenone and ethyl bromoacetate.     

Reaction of 2-allyloxy(thio)-4-methylquinolines with halogens

It was established that the halogenation of 2-allyloxy(thio)-4-methylquinolines leads to the formation of 3halogenomethyl-2, 3-dihydrooxazolo(thiazolo)[3, 2-a]quinolinium halides.Chelyabinsk State University, Chelyabinsk 454136. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1252–1254, September, 1996. Original article submitted July 7, 1996.     

Synthesis and study of N,N-disubstituted 4-[(4-aminophenyl)diazenyl]benzylidene-4'-alkylanilines

A series of N,N-disubstituted-4-[(4-aminophenyl)diazenyl]benzylidene-4'-alkylanilines (azo dyes) were synthesized from the reaction of the corresponding benzaldehyde with alkylanilines. These azo dyes exhibit nematic and SmC phases on heating. Their order parameter, photo-stability and miscibility were studied by investigation of a representative sample.     

Stereochemical studies of 5-methyl-3-(substituted phenyl)-5-[(substituted phenyl) hydroxy methyl]-2-thiooxazolidin-4-ones

The synthesis and stereochemical aspects of the aldol products, 5-methyl-3-(substituted phenyl)-5-[(substituted phenyl) hydroxy methyl]-2-thiooxazolidin-4-ones, are discussed.     

Synthesis of 2([Methyl-5-[(E)-2-aryl-1-ethenyl]-4-isoxazolyl]imino)-1,3-thiazolan-4-ones and Their Mannich Bases

Isoxazolyl chloroacetamides (2) were obtained from 4-amino-3-methyl-5-styrylisoxazoles (1) on reaction with chloroacetyl chloride. Cyclocondensation of 2 with NH₄SCN yielded 2([-methyl-5-(E)-2-aryl-1-ethenyl]-4-isoxazolylimino)-1,3-thiazolan-4-ones(3). Mannich reaction of 3 with formaldehyde and secondary amines gave isoxazolyl thiazolidinone Mannich bases (4 and 5).     

2-芳基-5-(4-硝基苯甲酰氨基)-1,3,4-噻二唑的合成

以芳甲酰肼和对硝基苯甲酰氯为主要原料, 合成出了10个酰氨基硫脲化合物5a～5j, 其中有6个(5d, 5f～5j)为新化合物. 在无需任何酸性催化剂条件下, 将制得的酰氨基硫脲在DMF中加热回流直接脱水关环合成出了9个2-芳基-5-(4-硝基苯甲酰氨基)-1,3,4-噻二唑化合物6a～6i, 其中7个(6b～6d, 6f～6i)为新化合物. 利用IR和1H NMR证明了化合物5存在两种异构体. 目标产物的结构通过IR, 1H NMR和元素分析进行了表征.     

A green approach for the electroorganic synthesis of 2-[(4-methyl-2-pyridyl)amino]-1,4-benzenediol derivatives in aqueous solution

The electrochemical synthesis of some new 2-[(4-methyl-2-pyridyl)amino)-1,4-benzenediol derivatives was performed via the electrochemical oxidation of hydroquinones in the presence of 2-amino-4-methylpyridine in an aqueous solution. The results demonstrate that electrogenerated p-benzoquinone participated in the Michael-type addition reaction via an electrochemical–chemical (EC) reaction mechanism pathway and converted to the corresponding 2-[(4-methyl-2-pyridyl)amino)-1,4-benzenediol derivatives. These new compounds have been synthesized in high yields and purity without using any toxic reagents or catalyst at the surface of carbon electrode.     

Synthesis and structural studies of (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}pyridin-2-yl)imino]butan-2-one oxime, ligand and its mono-, di- and trinuclear copper(II) complexes

A new dioxime ligand, (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}-pyridin-2-yl)imino]butan-2-one oxime, (H₂Pymdo) (3) has been synthesized in H₂O by reacting 2,3-butenedione monoxime (2) with 2,6-diaminopyridine. Mono-, di- and tri-nuclear copper(II) complexes of the dioxime ligand (H₂Pymdo) and/or 1,10-phenanthroline have been prepared. The dioxime ligand (H₂Pymdo) and its copper(II) complexes were characterized by ¹H-n.m.r., ¹³C-n.m.r. and elemental analyses, magnetic moments, i.r. and mass spectral studies. The mononuclear copper(II) complex of H₂Pymdo was found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu(II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The trinuclear copper(II) complex (6) was formed by coordination of the third Cu(II) ion with dianionic oxygen atoms of each of two molecules of the mononuclear copper(II) complexes. The data support the proposed structure of H₂Pymdo and its Cu(II) complexes.     

Crystal structure of 6-[(1-methyl-4-nitroimidazol-5-yl)thio] purine

6-[(l-methyl-4-nitroimidazol-5-yl)thio] purine, is an immunosuppressant derivative of the antitumour drug, 6-mercaptopurine. Crystals are monoclinic witha = 4.488(2),b = 31.886(4), c = 8.067(2)A and β= 105.99(2)° in the space group P2₁/c. The crystal structure was solved by direct methods using diffractometer data and refined by least squares to anR- index of 0.065 for 502 observed reflections. The molecule crystallizes in the N(9)-H tautomer form, in contrast to the N(7)-H tautomer form found in crystals of 6-mercaptopurine and assume a conformation in which the substituents on the sulphur atom are directed away from imidazole moiety of the purine NCL Communication number 3313     

Synthesis and mesomorphic properties on the series of 2-(4-alkylphenyl)-6-methylquinolines and 2-(4-alkoxyphenyl)-6-methylquinolines

Two homologous series of quinoline-containing liquid crystalline compounds were synthesised. Preparation of these compounds was completed in a short two-step reaction. Fair to good two-step overall yields of 63%–68%?and 50%–60%?were obtained respectively for the liquid crystalline compounds of 2-(4-alkylphenyl)-6-methylquinolines (nPQMe, n?=?4–8) and 2-(4-alkoxyphenyl)-6-methylquinolines (mOPQMe, m?=?3–7). Spectral analyses were in accordance with the expected structures. Polarising optical microscopy showed both series of compounds only display a nematic phase. Their thermotropic behaviours were further confirmed by differential scanning calorimetry.     

Synthesis and electrocatalytic properties of a dinuclear palladium(I) 1-[(2-bromo)benzene]-3-[(2-carboxymethyl)benzene]triazenide complex

The reaction of 1-[(2-bromo)benzene]-3-[(2-carboxymethyl)benzene]triazene and [Pd(CH₃CN)₄]Cl₂ gave a new dinuclear triazenido complex [Pd₂L₂] 1, which has been characterized by NMR spectra and X-ray crystallography. Electrochemical studies showed that complex 1 is capable of generating hydrogen from acetic acid in CH₂Cl₂.     

Synthesis and antimalarial effects of 5,6-dichloro-2-[(4-||4-(diethylamino)-i-methylbutyl] amino||-6-methyl-2-pyrirnidinyl)amino] benzimidazole and related benzimidazoles and lH-imidazo[4,5-b] pyridines

A group of fifty-five 2-[(4-11[(dialkylamino)alkyI]amino11-6-methyl-2-pyrimidinyl)amino]-benzimidazoles (VII) was synthesized in 3-88% yield by the condensation of the requisite 2-[(2-benzimidazolyl)amino]-4-chloro-6-methylpyrimidine (VI) with the appropriate polyamine in ethanol-hydrochloric acid or neat with excess amine containing potassium iodide. The 2-[(2-benzimidazolyl)amino]-6-methyl-4-pyrirnidinol precursors (V), obtained in 11-51% yield by cyclization of 2-(cyanoamino)-4-hydroxy-6-methylpyrimidine with a suitably substituted o-phenylenediamine, were chlorinated with phosphorus oxychloride to give the intermediate 2-[(2-benzimidazolyl)amino]-4-chloro-6-rnethylpyrimidines (VI) (27-99%). Oxidation of 5,6-dichloro-2-[(4-11[4-(diethylamino)-l-methylbutyl] amino 11-6-methyl-2-pyrimidinyl) amino ]benzimidazole ( 29 ) with m-chloroperbenzoic acid gave the distal N⁴'-oxide ( 31 ) (19%). Fusion of 2,3-uiaminopyridine with 2-(cyanoamino)-4-hydroxy-6-methylpyrimidine provided 2-[(4-hydroxy-6-tnethyl-2-pyrimidinyl)amino]-lH-imitlazo[4,5-b]pyrimidine (VIII) (30%), which upon chlori-nation with phosphorus oxychloride (63%) followed by amination with i N, N-diethylethylene-diamine afforded 2-(4-11[2-(diethylamino)ethyl] amino 11-6-methyl-2-pyrimidinyl)-lH-imidazo [4,5-b]pyridine (X) (8%). Thirty-eight of the novel 2-[(4-amino-6-methyl-2-pyrimidinyl)amino]-benzimidazoles possessed “curative” activity against Plasmodium berghei at single subcutaneous doses ranging from 20.640 mg./kg. Orally, thirty-one compounds exhibited suppressive activity against P. berghei comparable with or superior to the reference drugs 1-(p-chlorophenyl)-3-(4-11[2-(diethylarnino)ethyl]amino 11-6-methyl-2-pyrimidinyl)guanidine (I) and quinine hydrochloride, while twelve of them were 5 to 28 times as potent as I and quinine hydrochloride. Eight compounds also displayed strong suppressive activity against P. gallinaceum in chicks. 5,6-Dichloro-2-[(4-112-(diethylamino)ethyl]amino11-6-methyl-2-pyrimidinyl] benzimidazole (18) showed marked activity against a cycloguanil-resistant line of P. berghei, and the most promising member of the series, namely 5,6-dichloro-2-[(4-11[4-(diethylamino)-l-methylbutyl]amino11-6-methyl-2-pyrimidinyl)amino]benzimidazole ( 29 ) (Q = 28), was designated for preclinical toxico-logical studies and clinical trial. Structure-activity relationships are discussed.     

Novel amino- and thio(substituted)-1,4-naphthoquinone (NQ) compounds: Synthesis and characterization

Abstract

Synthesis of new 1,4-naphthoquinone derivatives is important in terms of searching new biologically active substances. In particular, compounds with piperazine and thiol moiety in their structure, show a wide range of pharmacological activity such as anti-inflammatory, anticancer, anti-fungal, anti-bacterial, anti-allergic, apoptosis and radical scavenging activities. In this study, new amino- and thio(substituted) naphthoquinone derivatives were synthesized by the reaction of thiols and thioalcohols with four naphthoquinone compounds which were used as starting materials. The new compounds were purified by column chromatography. The structure of the compounds was confirmed by different spectroscopic techniques.     

Synthesis,anti-inflammatory and analgesic activity of 2-[4-(substituted benzylideneamino)-5-(substituted phenoxymethyl)-4H-1,2,4-triazol-3-yl thio] acetic acid derivatives

The title compounds 3a–l have been synthesized by the reaction of thiocarbohydrazide with substituted phenoxy acetic acid to obtained substituted 1,2,4-triazoles (1). Compound 1 was treated with various substituted aromatic aldehydes which results in 4-(substituted benzylideneamino)-5-(substituted phenoxymethyl)-2H-1,2,4-triazol-3(4H)-thiones (2a–g), further 2a–g is converted to 2-[4-(substituted benzylideneamino)-5-(substituted phenoxymethyl)-4H-1,2,4-triazol-3-yl thio] acetic acid (3a–l) derivatives by the reaction with chloroacetic acid. All the newly synthesized compounds were evaluated for in vivo anti-inflammatory and analgesic activities. Among the series 2-[4-(2,4-dichlorobenzylideneamino)-5-(phenoxymethyl)-4H-1,2,4-triazol-3-yl thio] acetic acid (3d), 2-[4-(4-dichlorobenzylideneamino)-5-(phenoxymethyl)-4H-1,2,4-triazol-3-yl thio] acetic acid (3e), 2-[4-(2,4-dichlorobenzylideneamino)-5-[(2,4-dichlorophenoxy)methyl]-4H-1,2,4-triazol-3-yl thio] acetic acid (3j) and 2-[5-[(2,4-dichlorophenoxy)methyl)]-4-(4-chlorobenzylideneamino)-4H-1,2,4-triazol-3-yl thio] acetic acid (3k) showed significant anti-inflammatory activity with P < 0.001 (63.4%, 62.0%, 64.1% and 62.5% edema inhibition, respectively), as compared to the standard drug diclofenac (67.0%) after third hour respectively and also compounds 3j, 3k exhibited significant analgesic activity with P < 0.001 (55.9% and 54.9% protection, respectively) and less ulcerogenic activity as compared with standard drug aspirin (57.8%).     

Synthesis of 6,8-substituted 4-(hydroxyphenylamino)- and 4-(aminophenylamino)-2-methylquinolines

A procedure has been developed for the synthesis of 4-(hydroxyphenylamino)- and 4-(aminophenylamino)-2-methylquinolines having a substituent in the 6(8)-position of the quinoline ring from the corresponding 4-chloro-2-methylquinolines and o-, m-, and p-aminophenols and o-, m-, and p-phenylenediamines.     

Formation of 1-(2-aminophenyl)-5-ethoxy-4-methyl-3-phenylpyrazole and 4-methyl-3-phenylpyrazolo-[5,1-b]benzimidazole via an unusual enzotriazole ring opening

Successive treatment of N-[(1-ethoxy)alken-2-yl]benzotriazoles VII with butyllithium and trimethylsilyl chloride in TH-Fat — 78°C followed by refluxing in acidic acetone generated ring-opened 1-(2-aminophenyl)-5-ethoxy-4-methyl-3 phenylpyrazole VIII and 4-methyl-3 phenylpyrazolo[5, 1-b]benzimidazole IX.Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 775–780, June, 1996. Original article submitted May 14, 1996.     

Synthesis of aromatic polyethers by Scholl reaction. V. Synthesis and polymerization of 1,3-bis[4-(1-naphthoxy) benzoyl]benzene, 1,4-bis[4-(1-naphthoxy)benzoyl]benzene,bis[4-(1-naphthoxy)phenyl]methane, 1,3-bis[4-(1-naphthoxy) phenylmethyl]benzene,and 1,4-bis-[4-(1-naphthoxy)phenylmethyl]benzene

This article describes the synthesis and the cation-radical polymerization (Scholl reaction) of 1,3-bis[4-(1-naphthoxy) benzoyl] benzene ( 6 ) and 1,4-bis[4-(1-naphthoxy) benzoyl]- benzene ( 7 ) initiated by FeCI₃. This polymerization produced poly(ether ether ketone ketone)s (PEEKK) of number average molecular weight (M?_n) up to 5400 g/mol. The synthesis of bis[4-(1-naphthoxy) phenyl] methane ( 8 ), 1,3-bis[4-(1-napthoxy) phenylmethyl] benzene ( 9 ), and 1,4-bis[4-(1-naphthoxy) phenylmethyl] benzene ( 10 ) are also described. Polyethers of M?_n up to 15400 g/mol at a FeCl₃/monomer molar ratio of 2/1 were obtained. An increased polymerizability of the monomers 9 and 10 containing two CH₂ groups versus that of the corresponding monomers containing two carbonyl groups ( 6 and 7 ) was observed. This enhanced polymerizability was explained based on the increased nucleophilicity of monomers 9 and 10 .